A micromachining by a lithography using a photoresist composition has been conducted in a conventional manufacturing process of a semiconductor device such as an IC or LSI. Recently, an ultrafine pattern formation of a submicron region or a quarter micron region has been required as an integration level of an integrated circuit becomes higher. Accordingly, an exposure wavelength has a tendency to become shorter from g line to i line, and further to a KrF excimer laser ray. Furthermore, development of a lithography using an electron beam or X-ray or EUV ray other than the excimer laser ray is progressing.
These electron beam or X-ray or EUV ray lithography takes a seat as a pattern formation technique of the next generation or the next of the next generation, and a resist composition of a high sensitivity and high resolution is desired. Particularly, a high sensitization is very important problem to be solved for shortening of a processing time of wafer. However, when intending to a high sensitization, a resolution represented by a limiting resolution line width is reduced, so that development of a resist composition satisfying such characteristics is strongly desired.
The high sensitivity and the high resolution are in a relationship of tradeoff therebetween and thus it is very important how to satisfy them at the same time. As an actnic ray-sensitive or radiation-sensitive resin composition, there is a “positive type” actnic ray-sensitive or radiation-sensitive resin composition in which a resin poorly water-soluble or insoluble to an alkali developer is used to solubilize an exposed portion by a radiation exposure to form a pattern, and a “negative type” actnic ray-sensitive or radiation-sensitive resin composition in which a resin soluble to an alkali developer is used to make an exposed portion to be a poorly water-soluble or insoluble by a radiation exposure to form a pattern.
For the actnic ray-sensitive or radiation-sensitive resin composition suitable for such a lithography process using an electron beam, X-ray or EUV-ray, consideration is made mainly on a chemically amplified positive type resist composition using acid catalyzed reaction from the viewpoint of a high sensitization, and a chemical amplification type positive resist composition containing a phenolic resin (hereinafter, also referred to as a phenolic acid-decomposable resin), as a main component, which is insoluble or sparingly soluble in an alkali developer and becomes soluble by the action of an acid and an acid generator is effectively used.
In the meantime, forming a pattern that has various shapes such as a line, a trench, or a hole is requested in manufacturing a semiconductor device and the like. In order to satisfy the request for the formation of the pattern having various shapes, positive type as well as negative type actnic ray-sensitive or radiation-sensitive resin compositions have been developed, but a reduction of resolution is required in an ultrafine pattern formation. To solve such a problem, a method of developing a film obtained from an acid-decomposable resin with a developer other than an alkali developer is proposed (see, Patent Document 1).
Further, a method is known in which a film obtained from an electron beam resist containing a fullerene derivative is exposed, and subsequently, developed with the organic solvent to form a negative type pattern for the purpose of improving a dry etching resistance, resolution and sensitivity (see, for example, Patent Documents 2 and 3).
As other techniques in which a fullerene or the fullerene derivative is used in the resist composition, a method is also known in which a film is formed using a resist composition which contains a methanofullerene derivative having a specific structure, a photo-acid generator and a crosslinking agent, and an acid crosslinking reaction is performed by exposing the formed film, and then the film is developed with the organic solvent to form a negative type pattern (see, for example, Patent Document 4), or a method is known in which a film is formed using a resist composition formed by adding a predetermined amount of a fullerene derivative to a main chain scission type resist composition, the film is exposed, and then developed with the organic solvent to form a pattern (see, for example, Patent Document 5).
Further, in Patent Document 6, fullerene hydroxide exhibiting a high solubility in an ester solvent such as propylene glycol-1-monomethyl acetate (PGMEA) is disclosed as well as an application to a use of photoresist is suggested.
However, at present circumstances, a technique that can satisfy high sensitivity, high resolution, good roughness and good dry etching resistance at the same time is required.